Process of treating mineral oils.



C. J. GREENSTREET.

PROCESS OF TREATING MINERAL OtLS. APPLICATION FILED- MAR 31, I9I3. RENEWED AUG. 10.1918.

1,299, 17% Patented Apr. 1,1919.

TED STATES CHARLES JASON GREENSTREET, OF WEBSTER GROVES, MISSOURI, ASSIGNOR TO GASOLINE CORPORATION, OF NEW YORK, N. Y., A CORPORATION OF DELAWARE.

PROCESS OF TREATING MINERAL OILS.

Specification of Letters Patent.

Patented Apr. 1, 1919.

Application filed March 31, 1913, Serial No. 757,789. Renewed August 10, 1918. Serial No. M9330.

To all-whom it may concern Be it known that I, CHARLES J. GREEN- STREET, a citizen of the United States, and a resident of the city of Webster Groves, 1n the county of St. Louis and State of Missouri, have invented .a new and useful Process of Treating Minerak Oils, of which the following is a specification.

Heavy hydrocarbon oils, as usually refined, contain a greater or less percentage of the so-called vaselines, *which are solid or vention is to convert the solid and semisolid matter in the oil into normally liquid compounds without materially changing the character of the original ingredients of the oil.

I prefer to use the ordinary kerosene of commerce. This oil has a specific gravity of approximately forty-two to forty-five degrees Baum and contains an appreciable percentage of grease or semi-solid constituents, which will remain behind when the main volume of the oil is evaporated at ordinary atmospheric temperature. By my process, the keroseneis exposed, in a suitable medium and under other suitable conditions,

to the action of heat suflicient to break down the solid and semi-solid ingredients thereof into liquid hydrocarbons without affecting the constitution of the main body of the oil. In order that the process may be fully understood, I shall first describe an apparatus suitable for practising the same. I shall then describe the process as carried out with such apparatus under certain specified conditions, and shall afterward indicate qgeneral rules for'varying the conditions. he accompanying drawlng is a dlagrammatic view of an apparatus suitable for carrying out my process.

My apparatus comprises a furnace 1 in which is located a lon continuous coil of iron pipe 2. This pipe is of uniform diameter and free from abrupt angles, and the interior thereof is free from obstructions andabrupt changes of cross-sectional area. In actual practice I have used pipes of different diameters. used a pipe with an internal diameter of one inch, said pipe being fifty feet 'lon and coiled into a helix whose diameter is fifteen inches. Likewise, I have used a pipe of one and one-half inches diameter, one hundred feet long, and coiled into a helix of eighteen inches diameter.

The upper end of the heating coil is connected by pipe 3, atomizer 4, and pipe 5 to an oil supply tank 6. The atoinizer is an ordinary ejector. In'practice, I have had successful results with an atomizer wherein the steam pipe has an internal diameter of about one-quarter of an inch and terminates in a somewhat-smaller nozzle, the casing surrounding said pipe having a diameter of about one inch and one-quarter and communicating by a one-inch pipe with the oil supply tank.

The pipe 5 contains a cut-0H valve 7, whereby the oil supply tank 6 may be placed in communication with the heatin coil2, or out 01f therefrom, as desired.

of steam pressure and is provided with two branches 9 and 10. The branch 9 of the steam pipe opens into the ejector 4 through kabranch 11 containing a cut-ofi' valve 12 and a pressure gage 13; and said branch steam pipe 9 has a branch 14 communicating through a valve 15 with an oil burner 41. The second branch 10 of the steam pipe opens into the top of the oil supply tank 6 and is provided with a valved branch pipe 10? and with a cut-off valve 10. The tank 6 is provided with a pressure gage 10*.

The outlet end of the heating coil 2 comm'unicates through a pipe 16 with the upper end of a condenser coil 17 whose lower end is connected through a pipe 18 with a collecting tank or reservoir 19. This condenser coil 17 is kept cool by a bath of-water 20, in

I a tank 21 surrounding said coil. The col-' he pipe I 8 communicates'with a boiler or other source For instance, I have lecting tank or reservoir 19 communicates by a valved pipe 22 near its bottom with a pump 23. This pump 23 has an outlet or delivery pipe 24 which communicates through a valve 25 with a boiler or distillation chamber 26 having an outlet pipe 27 communicating with the upper end of a condenser coil 28 whose lower end communicates through a pipe 29 with a collection tank 30. This last mentioned condenser coil 28 is cooled by a bath of water 31 in a tank 32 surrounding said coil 28. The still 26 is heated by a furnace or heater 33 of any suitable construction.

In addition to the connections of the pump above mentioned, there is a pipe 34 extending from the lower portion of the still boiler and a valve 35 to a pipe 36 leading to the inlet side of the pump; and there is also a pipe 37 extending from the 'main delivery pipe 24 of the pump to the Oil supply tan 6 and containing a cut-off valve 38, whereby the oil in the still boiler 26 may be transferred to the oil supply tank 6 and re-run through the heating coil 2, when desired. The collection tanks 19 and 30 are provided with draw-off cocks 39 and 40, respectively,

near the bottoms thereof.

The furnace 1 is preferably heated by means of an oil burner 41. This oil burner is supplied through a pipe 42 containing a valve 43 and communicating with atank 44 containing a supply of untreated oil or other suitable fuel. A pipe 45 leads through a valve 46 from said fuel tank 44 to the pum inlet pipe 36, whereby the untreated oil may be run through the still and thence delivered into the oil supply tank 6. The fuel oil is vaporized by the jet of steam admitted through the steam pipe 14 into the fuel burner 41. The furnace 1 is provided with one or more pyrometers 47. The still tank is provided wit-h a draw-off ipe 48 pro-1. vided with a valve 49, Where y said tank may be emptied when desired.

In practical operation, steam from the source of supply is run through the heating coil 2 and said heating coil heated to a temperature in the neighborhood of one thousand degrees Fahrenheit, whereupon the oil is admitted into the coil under the pressure of the steam in the oil supply tank 6. In the case of the heating coil of one-inch interior diameter and fifty feet long, it is desirable to maintain a pressure of thirty-five to forty pounds per square inchon the oil and from forty-five to fifty pounds per square inch in the steam pipe. Under these conditions, kerosene'is run through the coil at the rate of a barrel of forty-two gallons in every six or nine minutes. 7

Under the conditions just stated, most of the solid and semi-solid matter in the oil is broken down into lighter hydro-carbons, which are liquid at ordinary atmospheric temperatures; but on account of the operation being effected in an atmosphere of steam and the very short duration of ex 0- sure to the action of the heat, the norma ly liquid hydrocarbons arenot afiected in appreciable quantity. The oil, which passes lection tank.

The oil collected in said collection tank or reservoir 19 is pumped periodically into the still boiler 26, which is operated at temperatures up to four hundred and eighty degrees Fahrenheit. The vapors from the still are condensed in the coil 28, and the resulting product accumulated in the collection tank 30, whence the oil may be drawn I off as desired. By filling the still boiler periodically and for each filling gradually increasing the temperature thereof up to 480 F. the ingredients of the oil may be separated according to gravity, the'lighter oils distilling over first and the heavier oils distilling later. In such case, the first and lighter product should be removed from the collection tank before the later and heavier product is received therein.

The oil remaining in the still boiler after cessation of the distillation due to the treatment at a temperature of four hundred and eighty degrees Fahrenheit, should be. pumped back into the oil tank 6 and re-run with the untreated oil through the heating coil. If any grease (that is, any Vaseline or solid or semi-solid hydrocarbons) should pass through the heating coil without beingv broken down, such grease will accumulate in the still and will thus be re-run through the heating coil.

In the above description, I have specified a temperature for the coil of approximately one thousand degrees Fahrenheit. This temv perature admits of considerable variation. The temperature must be high enough to break down the solid and semi-solid ingredients of the oil under the other conditions of the process, and the temperature should not be so high as to break down any con fifty degrees Fahrenheit nor in excess of eleven hundred and fifty degrees Fahrenheit; for in practical operation, lower temperature. is less efiective in breaking down the semi-solid matter, whereas the higher temperature is liable to break down the liquid hydrocarbons in appreciable quantity unless special precautions are taken to guard against such results.

When the process is successfully carried out, it is found that the product resulting therefrom is an oil whose specific gravity is very slightly lighter than that of the oil treated. In fact, the constitution of the main volume of the oil is not changed, but the solid and semi-solid ingredients thereof are merely broken down into like liquid hydrocarbons. Thus, starting with a kerosene of forty-five degrees Baum, the product should be an oil of approximately forty-six and fivetenths degrees 'Baum, which is fully volatile at atmospheric temperature without leaving a residue.

oil is drawn from the collection tank 19 and tested by comparison with a known standard product from oil of the kind undergoing treatment. Such a test may be made with the hydrometer; and if the product is too light, it indicates a breaking down of some of the liquid hydrocarbons, and therefore suggests that the temperature be lowered or that the pressure in the oil supply tank be increased to force the oil through the'coil more rapidly. Likewise, the sample may be poured out on to a sheet of paper, either alone or alongside of astandard sample, and the observed rate of evaporation will afford an indication similar to that of the hydrometer.

In "the foregoing description, I have described the process as practised with the coil of one-inch pipe. By .way of further illus- V tration, I will assume that the coil is a pipe of one and one-half inch internal diameter and one hundred feet long coiled into a helix with a diameter of eighteen inches. As the coil is longer, it requires more pressure to force the oil through at-the same speed, but a larger quantity of oil may be treated on account of the greater cross-sectional area. With a coil of the dimensions specified, I have had most successful results when the pressure on the oilin the supply tank is from fifty to sixty pounds per squareinch and In practice, it is desirable to have some degrees up to six hundred and fifty dethe temperature is lowered, the pressure should be lowered, so as to prolong the exposure of the oil to the heat.

While I have described the process as applied to ordinary kerosene of commerce, it is obvious that the process is applicable to the treatment of other heavy hydrocarbons.

The product resulting from the above described process is fully volatile at ordinary atmospheric temperature, and may therefore be used as a solvent for gums, resins, and similar materials and as the drying component for paints. It may also be used for all of the purposes for which kerosene is adapted; and in addition to such purposes, it may be used, as a fuel for gasolene burners of the common types and for incandescent lamps. In these latter cases, the new product has the advantage of burning longer and with a more intense heat than gasolene; and it likewise has the important advantage of being much less dangerous than gasolene. Another very important advantage is that the new product may be used as a fuel for intrnal combustion engines.

The product resulting from the foregoing treatment is free from all but a trace ofsulfur, and the various fractions thereof have boiling oints ranging'from three hundred to four undred and eighty degrees Fahrenheit, according to the gravity of the oil um dergoing treatment. Ifan oil heavier than kerosene is being operated on, there may remain in the still a large quantity of oil, (when the distillation temperature reaches four hundred and eighty degrees Fahrenheit. In such case, the residue maybe re-run through the heating coil as hereinbefore indicated; or such residue may be distilled at a higher temperature. In such case, the product of such increased distillation temperature will be an oil whose fractions boil at temperatures ranging from four hundred and eighty grees Fahrenheit.

What I claim as my invention and desire to secure by Letters Patent is:

- 1. The process of treating heavy hydrocarbon oil which consists in rapidly running the same commingled with steam through a continuous unobstructed coil of pipe kept at a temperature of from nine hundred to twelve hundred degrees Fahrenheit, the oil being exposed to the heat long enough to..-

break down the solid and semi-solid inv gradients thereof without afiecting a material quantity of the liquid ingredients, as hereinbefore described.

2. The process of treating heavy hydrocarbon oil which consists 1n running the 'same commingled with steam through a continuous unobstructed coil of pipe kept at a temperature of from nine hundred to twelve hundred degrees Fahrenheit, the oil being exposed to the action of the heat for .such time as would be required for a barrel of fifty-two gallons to pass through a pipe one and one-half inch diameter and one hundred feet long in from six to nine minutes:

3. The process of treating heavy hydrocarbon oil which consists in running the dred feet long in from six to nine minutes.

4. A hydrocarbon oil of a specific gravity of forty-eight degrees Baum or heavier volatile at ordinary atmospheric temperature without residue, said oil being produced from an oil of very slightly heavier specific gravity by the breaking down of its non-liquid ingredients and being characterized by the presence of olefin therein in larger quantity than in said heavier oil. 5. As an article of manufacture, the product resulting from the treatment of grease-containing kerosene at a temperature high enough to convert the grease into greaseless oil, but low enough to prevent the formation of naphtha and gasolene in appreciable amounts, as hereinbefore specified, said article being characterized by the mascara absence of grease and by being of only slightly lighter specific gravity than the initial kerosene.

6. The process of treating hydrocarbon oil containing a greasy hydrocarbon ingredient, which consists in passing the same, commingled with steam, through a coil of pipe at a temperature high enough to convert the greasy ingredient into liquid hydrocarbons, and low enough to prevent the formation of naphtha and gasolene inapprociable amounts.

7. The process oi. treating hydrocarbon oils having a portion of comparatively heavy constituent which consists in passing said oil through a passage at such temperature'and rate of flow' asto transform the heavier portion into lighter hydrocarbons without materially altering the other constituents of the oil under treatment.

8. The process of treating h drocarbon oils having a grease content whlch consists.

in passing said oil through a passage at such temperature and rate of flow that the cracking of the grease will occur without cracking the other and normally liquid ingredients of the oil.

CHARLES JASON GREENSTREET.

Witnesses:

W. E. WRISBERG, WM. F. Lnsomnv. 

